Preparation of polybenzimidazoles

ABSTRACT

A process for preparing polybenzimidazoles is disclosed in which aromatic bis-orthoaminosulfonamides and aromatic dicarboxylic acids or derivatives thereof are polymerized in polyphosphoric acid. The process provides thermally stable heterocyclic polymers of very high molecular weight that are especially useful in forming films and fibers.

United States Patent Arnold Aug. 26, 1975 i 1 PREPARATION OF POLYBENZIMIDAZOLES Primary Examiner.l0seph L. Schofer Assistant ExaminerMaria S. Tungol [75] inventor. Fred E. Arnold, Centerville, Ohio Attorney, Agent, or Firm Joseph E- Rusz; Cedric H [73] Assignee: The United States of America as Kuhn represented by the Secretary of the Air Force, Washington, DC. 22 Filed: Aug. 7, 1974 [571 ABSTRACT Appl. No.: 495,452

US. Cl... 260/78.4 R; 260/78.4 E; 260/78.4 N; 260/556 Int. Cl. COBF 18/16 Field of Search 260/78.4 R, 78.4 E, 78.4 N

References Cited FOREIGN PATENTS OR APPLICATIONS 9/l952 Canada 260/78.4 R

5 Claims, No Drawings PREPARATION OF POLYBENZIMIDAZOLES RIGHTS OF THE GOVERNMENT The invention described herein may be manufactured and used by or for the Government of the United States for all governmental purposes without the payment of any royalty.

FIELD OF THE INVENTION This invention relates to a process for preparing high molecular weight polybenzimidazoles. In one aspect the invention relates to a new monomer for use in preparing the polymers.

BACKGROUND OF THE INVENTION The conventional process for preparing polybenzimidazoles is disclosed by C. S. Marvel et al in U.S. Pat. No. 3,l74,974. As described in this patent, the process involves a two-stage procedure. In the first stage, the reactants are melt polymerized until a polymer of intermediate molecular weight is obtained. Thereafter, in the second stage of the process, the melt formed polymer is pulverized and subjected to solid state polymerization to produce a higher molecular weight. While this two-step process is the common commercial method for producing polybenzimidazoles, several difficulties are encountered in carrying out the method. The very nature of the two stages of this method, i.e., the melt polymerization step and the solid state powder polymerization step, makes temperature control an important factor. And it is difficult, if not impossible, to control the temperature so as to avoid erosslinking of the polymer. The process for preparing polybenzimidazoles is conducted in an inert atmosphere. During grinding of the prepolymer from the first step, air is absorbed on the surface of the prepolymer. The difficulty in effecting complete removal of this absorbed air before heating poses another disadvantage in the prior art process.

In U.S. Pat. No. 3,784,517. F. L. I-ledberg et al. disclose a process for preparing polybenzimidazoles that overcomes disadvantages of the above-described process. Thus, Hedberg et al describe a one-step process in which temperature control is unnecessary that comprises carrying out the polymerization in a reaction medium consisting essentially of an aromatic or aliphatic sulfone.

Both of the above-described processes utilize as a monomer fused tetraamines, such as l,2,4,5- tetraaminobenzene tetrahydrochloride, which exist in various hydrated forms and cannot be recrystallized to a high degree of purity. The free amine which is unstable to both air and light cannot withstand degradation so that the molecular weight of the products is limited.

It is an object of the present invention, therefore, to provide a process for preparing high molecular weight polybenzimidazoles.

Another object of the invention is to provide high purity bis-orthoaminosulfonamide monomers for use in the preparation of polybenzimidazoles.

Other objects and advantages of the invention will become apparent to those skilled in the art upon consideration of the accompanying disclosure.

SUMMARY OF THE INVENTION The present invention resides in a process for preparing polybenzimidazoles which comprises polymerizing in an inert atmosphere a bis-orthoaminosulfonamide and an aromatic dicarboxylic acid or derivative thereof, the polymerizing being conducted in polyphosphoric acid. The polymerization reaction involved is 5 shown by the following equation:

TosNH NHTos XAr'X NH NH,

I ll (l N H Ar Ar' wherein (Ill) n Ar IS I 1 8 Tos represents R80 with R being an aromatic, aliphatic or cycloaliphatic radical; Ar is an aromatic radi cal; and X is l -iioH. -o

CN or CONH The number (n) of the repeating units (III) is generally such that the polybenzimidazole has an intrinsic viscosity of 0.5 to 5 dl/g in 100 percent methanesulfonic acid.

The improvement obtained in preparing polybenzimidazoles by the present process lies, at least in part, in the discovery that the bis-orthoaminosulfonamides (compounds of formula I) can be purified by recrystallization to a very high degree, e.g., to within a half degree melting point. Furthermore, in contrast to conventionally employed tetraamines which are subject to degradation, it has been found that the monomers of this invention can be stored for extended periods of time without light and air oxidation. The stability of the monomers results from the fact that the oxygen of the sulfonamide group hydrogen bonds with the orthoamino protons which acts as an internal stabilizer.

Still further, the sulfonamide groups are quantitatively hydrolyzed to the free amine in the polymerization medium so that stoichiometry of the monomers in the process is not affected. Because of these several factors, use of the bis-orthoaminosulfonamides as monomers in the preparation of polybenzimidazoles makes it possible to prepare very high molecular weight polymers. For example. the use of l,3-diamino-4,6-(ptoluenesulfamido)benzene as a monomer replacement for l,2,4,5-tetraaminobenzene in the polymerization provides a polybenzimidazole having a molecular weight about six times greater than that reported in the literature lH. Vogel and C. S. Marvel, J. Polymer Sci., 50, 5ll(196l)].

ln formula (I) representing the bisorthoaminosulfonamides, Tos, an abbreviation for the expression tosylate," includes those sulfonamide derivatives represented by RSO in which R is an aromatic, aliphatic or cycloaliphatic radical, The aromatic, aliphatic and cycloaliphatic nuclei can have various hydrocarbon radicals substituted thereon, and the aromatic nuclei can also have halogen atoms, e.g., chlorine, bromine, iodine and fluorine, substituted thereon. Advantageously the hydrocarbon portion has no more than carbon atoms therein since larger groups, while still reactive, have a tendency to react sluggishly.

Typical sulfonamide derivative groups are those in which R is phenyl, tolyl, xylyl, naphthyl, diphenyl, methylnaphthyl, benzyl, chlorophenyl, chlorodiphenyl, methyl, ethyl, propyl, amyl, octyl, decyl, dodecyl, octadecyl, cyclohexyl cycloheptyl, methylcyclohexyl, ethylcycloheptyl, and the like.

The bis-orthoaminosulfonamides, which are new compounds, are generally synthesized by a two-stage procedure. In the first stage, bisorthonitrosulfonamides are formed by nitration of bissulfonamides while in the second stage the his orthoaminosulfonamides are produced by reduction of the first stage product. The reactions involved can be represented by the following equation in which Ar and Tos are as indicated hereinbefore:

Tos N H The nitration is carried out by adding nitric acid to acetic anhydride at a rate such as to maintain a temperature below about 5C. Upon completion of the addition, a bis-sulfonamide is added. The resulting reaction mixture is stirred at about room temperature for a period of about 8 to l6 hours. The precipitate that forms is recovered, e.g., by filtration, washed with water, and recrystallized from acetone to yield a purified bisorthonitrosulfonamide. In the reduction reaction, the bis-orthonitrosulfonamide, a reaction medium, such as N,N-dimethylacetamide, and a catalytic amount of a supported palladium catalyst are introduced into a pressure vessel. The vessel is then pressured with hydrogen for a period of about 8 to 16 hours. At the end of this period, the reaction mixture is filtered through a filter aid into a non-solvent for the product, such as diethyl ether. The precipitate that forms is recovered, e.g., by filtration, and air dried. Recrystallation from an alcohol, such as methanol, yields a high purity bisorthoaminosulfonamide.

In the preparation of bis-orthoaminosulfonamides in which R is pyridine, it is preferred to use a one-step procedure. This is possible because the selective reactivity of the 3,5-positions of tetraaminopyridine trihydrochloride allows the formation of the bisorthoaminosulfonamide directly by reaction with two moles of a sulfonyl chloride. In this process a sulfonyl chloride and 2,3,5,6-tetraaminopyridine trihydrochloride in a 2 to 1 mole ratio are added to a cooled reaction medium, such as pyridine. The reaction mixture is then stirred at room temperature for about 4 to 8 hours. Thereafter, the reaction mixture is poured into distilled water, thereby forming a precipitate. After separation of the precipitate, e.g., by filtration, it is recrystallized from an alcohol, such as ethanol, thereby giving a high purity bis-orthoaminosulfonamide. Examples of sulfonyl chlorides that can be used include toluene sulfonyl chloride, benzene sulfonyl chloride, xylyl sulfonyl chloride, naphthyl sulfonyl chloride, methyl sulfonyl chloride, ethyl sulfonyl chloride, propyl silfonyl chloride, cyclohexyl sulfonyl chloride, and the like.

As mentioned above, the aromatic dicarboxylic acids or derivatives thereof, which are used as comonomers, can be represented by the formula X-Ar'-X. Examples of suitable aromatic moieties (Ar') include 1,4- phenylene; 1,3-phenylene; 1,4-haphthalene; 1,6- naphthalene; 2,6-naphthalene', 2,5-pyridine; 2,5-

pyrazine', 2,5-furan, and the like. Furthermore, aromatic moieties can be employed in which the two X groups are on separate nuclei, the nuclei being joined by a carbon-to-carbon bond, a methylene group, an ether group or similar linking group. Examples of these latter aromatic moieties include 4,4'-diphenyl; 4,4- diphenylether; 4,4'-diphenylsulfide; 4,4- diphenylsulfone; 4,4'-diphenylmethane, and the like.

The compounds described in the preceding paragraph are well known compositions which are disclosed in the literature. Specific examples of such compounds include terephthalic acid, isophthalic acid,

N HTos TosN H N HTos Nitrzltion Ar Reduction naphthalenel ,4-dicarboxylic acid, naphthalene-1,6- dicarboxylic acid, naphthalene-2,-dicarboxylic acid, pyrazine-2,S-dicarboxylic acid, furan-2,5-dicarboxylic acid, quinoline-2,6-dicarboxylic acid, 4,4- biphenyldicarboxylic acid, diphenylether-4,4'- dicarboxylic acid, diphenylsulfide-4,4-dicarboxylic acid, diphenylmethane-4,4-dicarboxylic acid, diphenylsulfone-4,4-dicarboxylic acid, diphenylterephthalate, diphenylisophthalate,terephthalamide, isophthalamide, terephthalnitrile, isophthalnitrile, and the like.

In carrying out the process of this invention equimolar amounts of monomers (I) and (ll) are reacted in polyphosphoric acid in an inert atmosphere. Examples of suitable inert gases include nitrogen, helium and argon. initially, the reaction mixture is heated to and maintained at a temperature in the range of about 50 to C for a period of about 2 to 24 hours. During this period detosylation of the bis-orthoaminosulfonamide occurs. Thereafter, the reaction mixture is heated to and maintained at a temperature ranging from about to C for a period of about 6 to 24 hours. During this period polymerization is occurring to provide a high molecular weight polymer. At the end of the period, the polymer is recovered from solution by pouring the reaction mixture into a non-solvent for the polymer, such as distilled water or an alcohol. The polybenzimidazole product recovered has a very high molecular weight as indicated by its intrinsic viscosity. In order to purify the polymer, it is usually desirable to wash the product with an alcohol after which it is dried at an elevated temperature under reduced pressure. The dried polymer is then precipitated from a solvent, such as methane-sulfonic acid, and again dried to provide a purified product.

A more complete understanding of the invention can be obtained by referring to the following illustrative examples which are not intended, however, to be unduly limitative of the invention.

EXAMPLE 1 a. l,3-Dinitro-4,6-( p-toluenesulfamido)benzene To 100 ml of acetic anhydride was added dropwise ml of 70% nitric acid at a rate such as to maintain the temperature below 5C. After the addition was completed, 17 g (0.0445 mole) of 1,3-(ptoluenesulfamido)benzene was added at a rate such as to maintain the temperature below 15C. The solution was stirred at room temperature for 12 hours. The yellow precipitate that formed was collected, washed with water, and recrystallized from acetone to yield 18 g (80%) of the product, m.p. 2l32l5C.

Analysis: Calculated for C H N S O (Wt C,47.42; H,3.58; N,ll.05. Found (Wt C,47.46; H,3.37; N,l0.80.

b. 1,3-Diamino-4,6-(p-toluenesulfamido)benzene A Parr hydrogen pressure bomb was charged with 10 g (0.0197 mole) of 1,3-dinitro-4,6-(ptoluenesulfamido)bcnzene, 150 ml. of N,N- dimethylacetamide and 1 g of catalyst 10% palladium on powdered charcoal). The bomb was pressurized with hydrogen to 50 psi and allowed to shake for 12 hours. The reaction mixture was suction filtered through Celite filter aid into 1 liter of stirred diethyl ether. The resulting white precipitate was collected and air dried. Recrystallization from anhydrous methanol gave 7 g (80% yield) of product, m.p. 221221.5C.

Analysis: Calculated for C H N S- O C.53.79; H,4.96; N.12.54. Found: C,53.68; H.495; N,l2.29.

EXAMPLE 11 Poly[( 1,7-dihydrobenzol 1,2-d:4,5-d']diimidazole-2,6- diyl)- l ,4-phenylcne] To 100 g of deoxygenated polyphosphoric acid were added 1.15 g (0.00256 mole) of 1,3-diamino-4,6-(ptoluenesulfamido)benzene and 0.4279 g (0.00256 mole) of terephthalic acid. The mixture was slowly heated (4/min) to 90C and maintained at that temperature for 16 hours. The temperature was then increased at the same rate to 190C and maintained at that temperature for 6 hours. The resulting viscous solution was poured out of the flask at 190C into a beaker and allowed to cool to room temperature. The polymcr was precipitated in methanol, using a blender to facilitate mixing. The fibrous yellow material was washed twice with l-liter portions of anhydrous methanol and dried at 200C under reduced pressure (0.4 mm Hg). Precipitation from 500 g of methanesulfonic acid and drying in the above manner gave 0.8 g (93%) of polymer. An intrinsic viscosity of 4.9 dl/g in 100% methanesulfonic acid was determined.

Analysis: Calculated for (C H NJ C.72.41; H,3.45; H,24.14. Found: C,72.23; H.356; N,23.48.

EXAMPLE [1] a. 2,6-Dinitrol ,5(p-toluenesulfamido)naphthalene To 100 ml of acetic anhydride was added 15 ml of nitric acid at a rate sufficient to maintain the temperature below -10C. After the addition was completed, 10 g (0.021 mole) of l,5-(p-to1uenesulfamido)- naphthalene was added at a rate sufficient to maintain the temperature below 0C. The solution was stirred at room temperature for 12 hours. The yellow precipitate that formed was collected, washed with water, and recrystallized from methylene chloride to yield 4.0 g (35%) of the product, m.p. 235-236C.

Analysis: Calculated for C H, N S O C,5 1.78; H,3.62; N,l0.06. Found: C,5l.55; H.367; N,10.10.

b. 2,6-Diaminol ,S-(p-toluenesulfamido)naphthalene A Parr hydrogen pressure bomb was charged with 5 g (0.0089 mole) of 2,6-dinitro-1,5-(p-to1uenesulfanamido )naphthalene 100 ml of N,N- dimethylacetamide and 0.5 g of catalyst (10% palladium on powdered charcoal). The bomb was pressurized to 50 psi with hydrogen and allowed to shake for 12 hours. The reaction mixture was suction filtered through Celite filter aid into 2 liters of stirred diethyl ether. The resulting white precipitate was collected and air dried. Recrystallization from N,N- dimethylacetamide gave 3.75 g of the product, m.p. 261261.5C.

Analysis: Calculated for C H N,S O C,58.04; 11,4.87; N,11.28. Found: C,57.49; H,4.96; N,l 1.10.

EXAMPLE 1V Poly[( 1 ,4-dihydronaphtho[ l ,2-d:4,5-d'ldimidazole- 2,7-diyl )-l ,4-phenylene] To 100 g of deoxygenated polyphosphoric acid was added 1 g (2.0 mmoles) of 2.6-diamino-l,5-(ptoluenesulfamido)naphthalene and 0.348 g (2.1 mmoles) of terephthalic acid. The mixture was slowly heated (4/min) to C and maintained at that temperature for 12 hours. The temperature was then increased at the same rate to 190C and maintained at that temperature for 12 hours. The resulting solution was allowed to cool to room temperature and precipitated in methanol, using a blender to facilitate mixing. The fibrous yellow material was washed twice with 1- liter portions of anhydrous methanol and dried at 200C under reduced pressure (0.4 mm Hg). Precipitation from 200 g of methanesulfonic acid and drying in the above manner gave 0.59 g (99%) of polymer. An intrinsic viscosity of 2.2 dl/g in 100% methanesulfonic acid was determined.

Analysis: Calculated for (C H NQ C,76.58; H.357; N.19.84. Found: C,75.43; H,4.00; N,18.98.

EXAMPLE V 2,6-Diamino-3,5-( p-toluencsulfamido )pyridine To 100 ml of pyridine containing 7.24 g (0.038 moles) of p-toluencsulfonyl chloride. was added, as a powder, 5 g (0.019 mmole) of 2.3.5.6- tetraaminopyridine trihydrochloride monohydrate. The tetraamine was added to a cooled (5C) reaction medium. After the addition the reaction mixture was stirred at room temperature for 6 hours and then poured into I liter of distilled water. The white precipitate that formed was collected and recrystallized from 95% ethanol to afford 7.5 g (88%) of product, m.p. 242242.5C.

Analysis: Calculated for C H N S O C,50.98; H,4.73; N,l5.65. Found: C,50.93; H.484; N,l5.60.

EXAMPLE VI Poly[( l,7-dihydropyrido[1,2-d:4,S-d'ldiimidazo-2.6- diyl)-l ,4-phenylene] To 100 g of deoxygenated polyphosphoric acid were added 2 g (4.4 mmoles) of 2.6-diamino-3,5-(ptoluenesulfamido)pyridine and 0.742 g (4.4 mmoles) of terephthalic acid. The mixture was slowly heated (4lmin) to 50C and maintained at that temperature for 8 hours. The temperature was then increased at the same rate to 190C and maintained at that temperature for 6 hours. The resulting solution was allowed to cool to room temperature and precipitated into 2 liters of anhydrous methanol. The yellow material was dissolved in 500 g of methanesulfonic acid and reprecipitated in the above manner to give 1 g (98%) of polymer. An intrinsic viscosity of 0.75 dl/g in lO% methanesulfonic acid was determined.

Analysis Calculated for (C, H-,N C,66.94; H,3.02; N,30.03. Found: C,64.85; H.401; N,29.72.

As seen from the foregoing, the present process makes it possible to produce high molecular weight polybenzimidazoles. As previously mentioned, this improvement is attributable to the high purity bisorthoaminosulfonamides that are employed as monomers in the process.

As will be evident to those skilled in the art, modifications of the present invention can be made in view of the foregoing disclosure without departing from the spirit and scope of the invention.

I claim:

I. A process for preparing polybenzimidazoles which comprises reacting in polyphosphoric acid a mixture of an aromatic bis-orthoaminosulfonamide having the formula:

and Tos represents R with R being an aromatic, aliphatic or cycloaliphatic radical, and an aromatic dicarboxylic acid or derivative thereof having the formula:

-CN, or CONH and Ar is an aromatic radical.

2. The process according to claim 1 in which an equimolar mixture of the aromatic bisorthoaminosulfonamidc and the aromatic dicarboxylic acid or derivative thereof is initially heated to and maintained at a temperature in the range of about 50 to C for a period of about 2 to 24 hours after which the reaction mixture is heated to and maintained at a temperature in the range of about 170 to [C for a period of about 6 to 24 hours.

3. The process according to claim 2 in which the aromatic bis-orthoaminosulfonamide is l,3-diamino-4.6- (p-toluenesulfamido)benzene and the aromatic dicarboxylic acid is terephthalic acid.

4. The process according to claim 3 in which the aromatic bis-orthoaminosulfonamide is 2,6-diamino-l ,S-ptoluenesulfonamido)naphthalene and the aromatic dicarboxylic acid is terephthalic acid.

wherein X is 5. The process according to claim 3 in which the aro-' boxylic acid is terephthalic acid. 

1. A PROCESS FOR PREPARING POLYBENZIMIDAZOLES WHICH COMPRISES REACTING IN POLYPHOSPHORIC ACID A MIXTURE OF AN AROMATIC BIS-ORTHOAMINOSULFONAMIDE HAVING THE FORMULA:
 2. The process according to claim 1 in which an equimolar mixture of the aromatic bis-orthoaminosulfonamide and the aromatic dicarboxylic acid or derivative thereof is initially heated to and maintained at a temperature in the range of about 50* to 90*C for a period of about 2 to 24 hours after which the reaction mixture is heated to and maintained at a temperature in the range of about 170 to 195*C for a period of about 6 to 24 hours.
 3. The process according to claim 2 in which the aromatic bis-orthoaminosulfonamide is 1,3-diamino-4,6-(p-toluenesulfamido)benzene and the aromatic dicarboxylic acid is terephthalic acid.
 4. The process according to claim 3 in which the aromatic bis-orthoaminosulfonamide is 2,6-diamino-1,5-p-toluenesulfonamido)naphthalene and the aromatic dicarboxylic acid is terephthalic acid.
 5. The process according to claim 3 in which the aromatic bis-orthoaminosulfonamide is 2,6-diamino-3,5-(p-toluenesulfamido)pyridine and the aromatic dicarboxylic acid is terephthAlic acid. 